Hairdye composition

ABSTRACT

A hairdye composition, characterized in that, indoline and/or indoline compound and laccase are compounded.

This application is the national phase under 35 U.S.C. §371 of PCTInternational Application No. PCT/JP00/04089 which has an Internationalfiling date of Jun. 22, 2000 which designated the United States ofAmerica, the entire contents of which are hereby incorporated byreference.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a hairdye composition containingindoline and/or indoline compound and laccase and, more particularly, itrelates to an oxidative hairdye composition having little skinirritation, a good stability with a lapse of time, an excellenthair-dyeing effect, an excellent usability and particularly an abilityof being prepared as a single preparation type.

BACKGROUND ART

Usually, an oxidative hairdye contains an oxidation dye (the firstpreparation) and an oxidizing agent (the second preparation) and, uponuse, they are mixed to react and are applied to hair whereby white hairis dyed. When a commercially available oxidative hairdye is used, thereis a risk of causing a rash because p-phenylenediamine, p-aminophenol,etc. compounded in the first preparation are skin-sensitive substances.On the other hand, with regard to the composition for the secondpreparation, most of it uses hydrogen peroxide as an oxidizing agentand, therefore, there is a possibility of damage of hair and skin.

Under such circumstances, indole compounds and indoline compounds havebeen proposed as substitutes for the conventional oxidation dyes(Japanese Laid-Open Patent Hei-8/40857) but the present situation isthat using only such substances results in poor hair dyeing. On theother hand, as attempts for reducing the damage of hair by hydrogenperoxide, various means using an oxidase has been proposed. Examples ofsuch an art are the use of laccase (U.S. Pat. No. 3,251,742 and JapaneseLaid-Open Patent Hei-6/172145), the use of peroxidase (JapaneseLaid-Open Patents Sho-47/10400 and Sho-53/32132) and the use of uricase(Japanese Laid-Open Patent Sho-63/246313). However, in most of the artdisclosed herein, hydrogen peroxide is added or hair dyeing is conductedby effective utilization of hydrogen peroxide due to the characteristicfeature of the enzyme whereby elimination of the problem by hydrogenperoxide is not fundamentally solved. Further, in the case of laccase,due to its unstable property during preservation, when it is compoundedin the composition, reaction of oxygen with an oxidation dye in aheadspace takes place whereupon insoluble aggregates are formed.Formation of such insoluble aggregates in a product is a very bigproblem as a hairdye. Accordingly, there is a big problem that it cannotbe put on a market as a product unless such insoluble matters aresuppressed.

DISCLOSURE OF INVENTION

The present invention has been accomplished under the above-mentionedcircumstances and an object of the present invention is to offer anoxidative hairdye composition having little skin sensitivity, a goodstability with a lapse of time, an excellent hair dyeing effect and anexcellent usability.

In order to achieve the above-mentioned object, the present inventorshave conducted an intensive study for achieving the above-mentionedobject, found that an oxidative hairdye composition having little skinirritation, an excellent hair dyeing effect, a good stability even bypreparing into a single preparation type and an excellent usability canbe obtained when indoline and/or indoline compound and laccase arejointly used and have now achieved the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

When the present invention is illustrated in detail, indoline and/orindoline compound as developer(s) and laccase as an oxidizing agent arecompounded in a hairdye composition of the present invention.

Examples of indoline and indoline compound are indoline,5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline,N-ethyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline,4-hydroxy-5-methoxyindoline, 6-hydroxy-7-methoxyindoline,6,7-dihydroxyindoline, 4,5-dihydroxyindoline,4-methoxy-6-hydroxyindoline and salts thereof and each of them may beused either solely or two or more of them may be used jointly.

The compounding concentration of indoline and/or indoline compound inthe composition of the present invention varies depending upon thefrequency of use and the dosage form but, usually, it is 0.01-30% (% byweight; hereinafter, % will be used in the same sense) or, preferably,0.05-20%.

When color change is desired in the hair dye composition of the presentinvention, a small amount of oxidation dye may be used as a coupler.Known couplers may be used as such an oxidation dye. For example, thosewhich are described in “Standards for Materials for Quasi-Drugs,” suchas 5-amino-o-cresol, o-aminophenol, m-aminophenol, p-aminophenol,2,6-diaminopyridine, 5-(2-hydroxylethylamino)-2-methylphenol,N,N-bis(β-hydroxyl)-p-phenylenediamine sulfate,p-nitro-o-phenylenediamine, p-phenylenediamine, m-phenylenediamine,N-phenyl-p-phenylenediamine, resorcinol,2-hydroxyl-5-nitro-2′,4′-diaminoazobenzene sodium sulfate,toluene-2,5-diamine, 5-amino-o-cresol sulfate, p-aminophenol sulfate,o-chloro-p-phenylenediamine sulfate, 4,4′-diaminodiphenylamine sulfate,p-methylaminophenol sulfate, p-phenylenediamine sulfate,m-phenylenediamine sulfate, toluene-2,5-diamine sulfate,2,4-diaminophenoxyethanol hydrochloride, toluene-2,5-diaminehydrochloride, m-phenylenediamine hydrochloride, 2,4-diaminophenolhydrochloride, 3,3′-iminodiphenol, p-phenylenediamine hydrochloride,N-phenyl-p-phenylenediamine hydrochloride, N-phenyl-p-phenylenediamineacetate, 1,5-dihydroxynaphthalene, toluene-3,4-diamine,p-methylaminophenol,N,N′-bis(4-aminophenyl)-2,5-diamino-1,4-quinonediimine, o-aminophenolsulfate, 2,4-diaminophenyl sulfate and m-aminophenol sulfate, may beused in an appropriate amount either solely or jointly by combining twoor more.

Further, direct materials which are frequently used together with suchoxidation dyes such as 2-amino-4-nitrophenol, 2-amino-5-nitrophenol,1-amino-4-methylaminoanthraquinone, nitro-p-phenylenediaminehydrochloride, 1,4-diaminoanthraquinone, nitro-p-phenylenediamine,picramic acid, sodium picramate, 2-amino-5-nitrophenol sulfate,nitro-p-phenylenediamine sulfate, p-nitro-o-phenylenediamine sulfate andp-nitro-m-phenylenediamine sulfate may be used as well.

Such a coupler may be used only when color of the dyed hair is to bechanged and, in that case, its compounding concentration in thecomposition is 0.001-5% or, preferably, 0.005-2%. WO 99/36034, WO99/36035, WO 99/36036, WO 99/36037, WO 99/36038, WO 99/36039, WO99/36040, WO 99/36041, WO 99/36042, WO 99/36043, WO 99/36044, WO99/36045 and WO 99/36046 in the name of L'Oreal discloses different kindof oxidizing dyes (developed substances or oxidation bases) and couplingcomponents (coupling agents) which can also be used according to thepresent invention and which are hereby incorporated by reference.

The oxidation bases can in particular be selected amongpara-phenylenediamines, double bases, para-aminophenols,ortho-aminophenols and heterocyclic oxidation bases.

Among the para-phenylenediamines suitable as oxidation bases in the dyecompositions according to the invention, the following compounds of theformula (1) and their addition salts with an acid can in particular bementioned:

in which

R¹ represents a hydrogen atom, C₁-C₄-alkyl, C₁-C₄-monohydroxyalkyl,C₂-C₄-polyhydroxyalkyl, (C₁-C₄ )alkoxy(C₁-C₄)alkyl, C₁-C₄-alkylsubstituted with a nitrogen-containing group, phenyl or 4′-aminophenyl;

R² represents a hydrogen atom, C₁-C₄-alkyl, C₁-C₄monohydroxyalkyl,C₂-C₄polyhydroxyalkyl, (C₁-C₄)alkoxy(C₁-C₄)alkyl or C₁-C₄alkylsubstituted with a nitrogen-containing group;

R³ represents a hydrogen atom, a halogen atom such as chlorine, bromine,iodine or fluorine, C₁-C₄alkyl, C₁-C₄monohydroxyalkyl,C₁-C₄hydroxyalkoxy, C₁-C₄acetylaminoalkoxy, C₁-C₄mesylaminoalkoxy orC₁-C₄carbamoylaminoalkoxy,

R⁴ represents a hydrogen atom, a halogen atom or C₁-C₄-alkyl.

Among the nitrogen-containing groups in the above formula (1), amino,mono(C₁-C₄)alkylamino, di(C₁-C₄)alkylamino, tri(C₁-C₄ )alkylamino,monohydroxy(C₁-C₄)alkylamino, imidazolinium and ammonium can inparticular be mentioned.

More particularly among the para-phenylenediamines of the above formula(1), the following para-phenylenediamines can be mentioned:para-phenylenediamine, paratoluylenediamine, 2-chloropara-phenylenediamine, 2,3-dimethyl para-phenylenediamine, 2,6-dimethylpara-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,5-dimethylpara-phenylenediamine, N,N-dimethyl para-phenylenediamine, N,N-diethylpara-phenylenediamine, N,N-dipropyl para-phenylenediamine, 4-aminoN,N-diethyl 3-methyl aniline, N,N-bis(β-hydroxyethyl)para-phenylenediamine, 4-N,N-bis-(β-hydroxyethyl)amino 2-methyl aniline,4-N,N-bis-(β-hydroxyethyl)amino 2-chloro aniline, 2-p-hyroxyethylpara-phenylenediamine, 2-fluoro para-phenylenediamine, 2-isopropylpara-phenylenediamine, N-(β-hydroxypropyl) para-phenylenediamine,2-hydroxymethyl para-phenylenediamine, N,N-dimethyl 3-methylpara-phenylenediamine, N,N-(ethyl, β-hydroxyethyl)para-phenylenediamine, N-(β, γ-dihydroxypropyl) para-phenylenediamine,N-(4′-aminophenyl) para-phenylenediamine, N-phenylpara-phenylene-diamine, 2-β-hydroxyethyloxy para-phenylenediamine,2-β-acetylaminoethyloxy para-phenylenediamine, N-(β-methoxyethyl)para-phenylenediamine and their addition salts with an acid.

Among the para-phenylenediamines of the above formula (1), the followingare especially preferred: para-phenylenediamine, paratoluylenediamine,2-isopropyl para-phenylenediamine, 2-β-hydroxyethylpara-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine,2,6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine,2,3-dimethyl para-phenylenediamine, N,N-bis-(β-hydroxyethyl)para-phenylenediamine, 2-chloro para-phenylenediamine,2-β-acetylaminoethyloxy para-phenylenediamine and their addition saltswith an acid.

By double bases is, according to the invention, meant such compositionswhich include at least two aromatic nuclei carrying amino and/orhydroxyl groups.

Among the double bases suitable as oxidation bases in the dyecompositions according to the invention, the compounds of the followingformula (2) and their addition salts with an acid can in particular bementioned:

in which

Z¹ and Z², which are identical or differ, represent a hydroxyl group or—NH₂, which can be substituted with a C₁-C₄alkyl group or with abridging group Y;

the bridging group Y is a linear or branched alkylene chain with 1 to 14carbon atoms, which can be interrupted or terminated by one or morenitrogen-containing groups and/or one or more hetero atoms, such asoxygen, sulphur or nitrogen atoms, and optionally be substituted withone or more hydroxyl groups or C₁-C₆-alkoxy groups;

R⁵ and R⁶represents a hydrogen or halogen atom, C₁-C₄alkyl,C₁-C₄mono-hydroxyalkyl, C₂-C₄polyhydroxyalkyl, C₁-C₄aminoalkyl or abridging group Y;

R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹², which are identical or differ, represent ahydrogen atom, a bridging group Y or a C₁-C₄alkyl group;

whereby it should be understood that the compounds of the formula (2)only include a single bridging group Y per molecule.

Among nitrogen-containing groups of the above formula (2), the followingcan in particular be mentioned: amino, mono(C₁-C₄)alkylamino,di(C₁-C₄)alkyl-amino, tri(C₁-C₄)alkylamino, monohydroxy(C₁-C₄)alkylamino, imidazolinium and ammonium.

Among the double bases of the above formula (2), the following can moreparticularly be mentioned: N,N=-bis-(β-hydroxyethyl)N,N′-bis-(4′-aminophenyl) 1,3-diamino propanol,N,N=-bis-(β-hydroxyethyl) N,N=-bis-(4′-aminophenyl) ethylenediamine,N,N=-bis-(4-aminophenyl) tetramethylenediamine,N,N′-bis-(β-hydroxyethyl) N,N′-bis-(4-aminophenyl)tetramethylenediamine, N,N′-bis-(4-methylaminophenyl)tetramethylenediamine, N,N′-bis-(ethyl) N,N′-bis-(4′-amino,3-methylphenyl) ethylenediamine,1,8-bis-(2,5-diaminophenoxy)-3,5-dioxaoctane and their addition saltswith an acid.

Particularly preferred double bases of the formula (2) areN,N′-bis-(β-hydroxyethyl) N,N′-bis-(4′-aminophenyl) 1,3-diaminopropanol, 1,8-bis-(2,5-diamino-phenoxy)-3,5-dioxaoctane or one of theiraddition salts with an acid.

Among the para-aminophenols suitable as oxidation bases in the dyecompositions according to the invention, the compounds of the followingformula (3) and their addition salts with an acid can especially bementioned:

in which

R¹³ represents a hydrogen or halogen atom, C₁-C₄alkyl,C₁-C₄monohydroxyalkyl, (C₁-C₄ )alkoxy(C₁-C₄ )alkyl, C₁-C₄aminoalkyl or(C₁-C₄)hydroxyalkyl(C₁-C₄)aminoalkyl,

R¹⁴ represents a hydrogen or halogen atom, C₁-C₄alkyl,C₁-C₄monohydroxyalkyl, C₂-C₄polyhydroxyalkyl, C₁-C₄aminoalkyl, C₁-C₄cyanoalkyl or (C₁-C₄)alkoxy(C₁-C₄)alkyl, whereby it should be understoodthat at least one of the groups R¹³ or R¹⁴ represents a hydrogen atom.

Among the para-aminophenols of the above formula (3), the following canin particular be mentioned: para-aminophenol, 4-amino 3-methyl phenol,4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethylphenol, 4-amino 2-aminomethyl phenol, 4-amino 2-(β-hydroxyethylaminomethyl) phenol, 4-amino 2-fluoro phenol and acid addition saltsthereof.

Among the ortho-aminophenols suitable as oxidation bases in the dyecompositions according to the invention, the following can in particularbe mentioned: 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methylphenol, 5-acetamido 2-amino phenol and acid addition salts thereof.

Among the heterocyclic bases suitable as oxidation bases in the dyecompositions according to the invention, the following can in particularbe mentioned: pyridine derivatives, pyrimidine derivatives, pyrazolederivatives, pyrazolo-pyrimidine derivatives and acid addition saltsthereof.

Among the pyridine derivatives, the compositions described for instancein the patents GB-PS 1 026 978 and GB-PS 1 153 196 can in particular bementioned: 2,5-diamino pyridine, 2-(4-methoxyphenyl)amino 3-aminopyridine, 2,3-diamino 6-methoxy pyridine, 2-(β-methoxyethyl)amino3-amino 6-methoxy pyridine, 3,4-diamino pyridine and the addition saltsthereof.

Among the pyrimidine derivatives, the compositions described forinstance in the German patent DE 2 359 399 or the Japanese patents JP88-169 571 and JP 91-333 495 or in the Patent Application WO 96/15765can in particular be mentioned: 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine,2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and theiraddition salts with an acid.

Among the pyrazole derivatives, the compounds described for instance inthe patents DE 3 843 892 and DE 4 133 957 and in the Patent ApplicationsWO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 can inparticular be mentioned: 4,5-diamino 1-methyl pyrazole, 3,4-diaminopyrazole, 4,5-diamino 1-(4′-chlorobenzyl) pyrazole, 4,5-diamino1,3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole,4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1,3-dimethyl 5-hydrazinopyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methylpyrazole, 4,5-diamino 1-(β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino1-ethyl 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-(4′-methoxyphenyl)pyrazole, 4,5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole, 4-amino5-(2′-aminoethyl)amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole,1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylaminopyrazole, 3,5-diamino 4-(β-hydroxyethyl)amino-1-methyl pyrazole andtheir acid addition salts.

Among the pyrazolo pyrimidine derivatives, the following can inparticular be mentioned: the pyrazolo-[1,5-a]-pyrimidines of the formula(4) shown below, their addition salts with an acid or base and theirtautomeric forms when a tautomeric equilibrium exists:

in which

R¹⁵, R¹⁶, R¹⁷ and R¹⁸, which are identical or differ, represent ahydrogen atom, C₁-C₄alkyl, aryl, C₁-C₄hydroxyalkyl,C₂-C₄polyhydroxyalkyl, (C₁-C₄)alkoxy(C₁-C₄)alkyl, C₁-C₄aminoalkyl (wherethe amine can be protected by an acetyl, ureido or sulfonyl group),(C₁-C₄)alkylamino (C₁-C₄)alkyl, di-[(C₁-C₄)alkyl] amino C₁-C₄alkyl(where the dialkyl groups can form a carbon ring or a heterocyclic ringwith 5 or 6 members), hydroxy-C₁-C₄alkyl or di-[hydroxy(C₁-C₄)alkyl]-amino C₁-C₄alkyl;

the groups X, which are identical or differ, represent a hydrogen atom,C₁-C₄alkyl, aryl, C₁-C₄hydroxyalkyl, c₂-c₄polyhydroxyalkyl, aminoC₁-C₄alkyl, (C₁-C₄)alkyl(C₁-C₄)aminoalkyl, di-[(C₁-C₄)alkyl]aminoC₁-C₄alkyl (where the dialkyl groups can form a carbon ring or aheterocyclic ring with 5 or 6 members), hydroxy (C₁-C₄)alkyl ordi-[hydroxy(C₁-C₄)alkyl]amino-C₁-C₄alkyl, amino, C₁-C₄alkyl ordi-[(C₁-C₄)alkyl]-amino, a halogen atom, a carboxylic acid group or asulfonic acid group;

i is 0, 1, 2 or 3;

p is 0 or 1;

q is 0 or 1;

n is 0 or 1;

with the proviso that

the sum p+q differs from 0;

when p+q is 2, n has the value 0, and the groups NR¹⁵R¹⁶ and NR¹⁷R¹⁸occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);

when p+q is 1, n has the value 1, and the group NR¹⁵R¹⁶ (or NR¹⁷R¹⁸) andthe group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7).

When the pyrazolo-[1,5-a]-pyrimidines of the above formula (4) are suchwhich include a hydroxyl group in one of the positions 2, 5 or 7 in theα-position to a nitrogen atom, a tautomeric equilibrium exists which forinstance can be indicated by the following reaction scheme.

Among the pyrazolo-[1,5-a]-pyrimidines of the above formula (4), thefollowing can be mentioned in particular:

pyrazolo-[1,5-a]-pyrimidine-3,7-diamine;

2,5-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine;

pyrazolo-[1,5-a]-pyrimidine-3,5-diamine;

2,7-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,5-diamine;

2,73-amino pyrazolo-[1,5-a]-pyrimidine-7-ol;

3-amino pyrazolo-[1,5-a]-pyrimidine-5-ol;

2-(3-amino pyrazolo-[1,5-a]-pyrimidine-7-ylamino)-ethanol;

2-(7-amino pyrazolo-[1,5-a]-pyrimidine-3-ylamino)-ethanol;

2-[(3-amino-pyrazolo[1,5-a]pyrimidine-7-yl)-(2-hydroxy-ethyl)-amino]ethanol;

2-[(7-amino-pyrazolo[1,5-a]pyrimidine-3-yl)-(2-hydroxy-ethyl)-amino]ethanol;

5,6-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine;

2,6-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine;

2,5, N 7, N 7-tetramethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine; andtheir addition salts and tautomeric forms, provided a tautomericequilibrium exists.

The pyrazolo-[1,5-a]-pyrimidines of the above formula (4) can beprepared by way of cyclisation of an aminopyrazole according to thesyntheses described in the following references:

EP 628559 BEIERSDORF-LILLY

R. Vishdu, H. Navedul, Indian J. Chem., 34b (6), 514, 1995.

N. S. Ibrahim, K. U. Sadek, F. A. Abdel-Al, Arch. Pharm., 320, 240,1987.

R. H. Springer, M. B. Scholten, D. E. O'Brien, T. Novinson, J. P.Miller, R. K. Robins, J. Med. Chem., 25, 235, 1982.

T. Novinson, R. K. Robins, T. R. Matthews, J. Med. Chem., 20, 296, 1977.

US 3907799 ICN PHARMACEUTICAL

The pyrazolo-[1,5-a]-pyrimidines of the above formula (4) canfurthermore be produced by cyclisation from a hydrazine according to thesyntheses described in the following references:

A. McKillop, R. J. Kobilecki, Heterocycles, 6(9), 1355, 1977.

E. Alcade, J. DeMendoza, J. M. Marcia-Marquina, C. Almera, J. Elguero,J. Heterocyclic Chem., 11(3), 423, 1974.

K. Saito, I. Hori, M. Higarashi, H. Midorikawa, Bull. Chem. Soc. Japan,47(2), 476, 1974.

The oxidation base or bases represent preferably between approximately0.0005% and approximately 12% by weight of the total weight of the dyecomposition according to the invention, especially between approximately0.005% and approximately 6% by weight.

The coupling agent or coupling agents suitable in the ready-to-use dyecompositions according to the invention are such which areconventionally used in oxidation dye composition, viz. metaphenylenediamines, metaaminophenols, metadiphenols, heterocyclic coupling agentsand their addition salts with an acid.

These coupling agents can especially be selected among2-methyl-5-amino-phenol, 5-N-(β-hydroxyethyl)-amino-2-methyl-phenol,3-amino-phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methyl-benzene,4-chloro-1,3-dihydroxy-benzene,2,4-diamino-1-(β-hydroxyethyloxy)-benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxy-benzene, 1,3-diamino-benzene,1,3-bis-(2,4-diaminophenoxy)-propane, sesamol, α-naphtol,6-hydroxy-indole, 4-hydroxy-indole, 4-hydroxy-N-methyl-indole,6-hydroxy-indolin, 2,6-dihydroxy-4-methyl-pyridine,1-H-3-methyl-pyrazole-5-on, 1-phenyl-3-methyl-pyrazole-5-one,2,6-dimethyl-pyrazolo-[1,5-b]-1,2,4-triazole,2,6-dimethyl-[3,2-c]-1,2,4-triazole,6-methyl-pyrazolo-[1,5-a]-benzimidazole and acid addition salts thereof.

The meta-aminophenol or meta-aminophenols applicable as coupling agentsin the ready-to-use dye composition according to the invention is/arepreferably selected from compounds of the following formula (5) and acidaddition salts thereof:

in which

R¹⁹ represents a hydrogen atom, C₁-C₄-alkyl, C₁-C₄monohydroxyalkyl orC₂-C₄polyhydroxyalkyl,

R²⁰ represents a hydrogen atom, C₁-C₄alkyl, C₁-C₄alkoxy or a halogenatom selected from chlorine, bromine and fluorine,

R²¹ represents a hydrogen atom, C₁-C₄alkyl, C₁-C₄alkoxy,C₁-C₄mono-hydroxyalkyl, C₂-C₄polyhydroxyalkyl, C₁-C₄monohydroxyalkoxy orC₂-C₄poly-hydroxyalkoxy.

Among the meta-aminophenols of the above formula (5), the following canbe mentioned in particular: meta-aminophenol, 5-amino-2-methoxy phenol,5- amino-2-(β-hydroxyethyloxy)-phenol, 5-amino-2-methyl phenol,5-N-(β-hydroxyethyl)amino-2-methyl phenol,5-N-(β-hydroxyethyl)amino-4-methoxy-2-methyl phenol,5-amino-4-methoxy-2-methyl phenol, 5-amino-4-chloro-2-methyl phenol,5-amino-2,4-dimethoxy phenol, 5-(γ-hydroxypropylamino)-2-methyl phenoland acid addition salts thereof.

The meta-phenylenediamine or meta-phenylenediamines applicable ascoupling agents in the ready-to-use dye composition according to theinvention is/are preferably selected from compounds of the followingformula (6) and acid addition salts thereof:

in which

R²² represents a hydrogen atom, C₁-C₄alkyl, C₁-C₄monohydroxyalkyl orC₂-C₄polyhydroxyalkyl;

R²³ and R²⁴, which are identical or differ, each represents a hydrogenatom, C₁-C₄alkyl, C₁-C₄monohydroxyalkoxy or C₂-C₄polyhydroxyalkoxy;

R²⁵ represents a hydrogen atom, C₁-C₄alkoxy, C₁-C₄aminoalkoxy,C₁-C₄mono-hydroxyalkoxy, C₂-C₄polyhydroxyalkoxy or2,4-diaminophenoxyalkoxy.

Among the meta-phenylenediamines of the above formula (6), the followingcan in particular be mentioned: 2,4-diamino-benzene,3,5-diamino-1-ethyl-2-methoxybenzene, 3,5-diamino-2-methoxy-1-methylbenzene, 2,4-diamino-1-ethoxybenzene, 1,3-bis-(2,4-diaminophenoxy)propane, bis-(2,4-diaminophenoxy)-methane,1-(β-aminoethyloxy)-2,4-diamino-benzene,2-amino-1-(β-hydroxy-ethyloxy)-4-methylamino-benzene,2,4-diamino-1-ethoxy 5-methyl-benzene,2,4-diamino-5-(β-hydroxyethyloxy)-1-methylbenzene,2,4-diamino-1-(β,γ-dihydroxy-propyloxy) benzene,2,4-diamino-1-(β-hydroxyethyloxy)-benzene,2-amino-4-N-(β-hydroxyethyl)-amino-1-methoxy-benzene and acid additionsalts thereof.

The meta-diphenol or meta-diphenols applicable as coupling agents in theready-to-use dye composition according to the invention is/arepreferably selected from the compounds of the following formula (7) andacid addition salts thereof:

in which

R²⁶ and R²⁷, which are identical or differ, each represents a hydrogenatom, C₁-C₄alkyl or a halogen atom selected from chlorine, bromine andfluorine.

Among the meta-diphenols of the above formula (7), the following can inparticular be mentioned: 1,3-dihydroxy-benzene,2-methyl-1,3-dihydroxy-benzene, 4-chloro-1,3-dihydroxy-benzene,2-chloro-1,3-dihydroxybenzene, and acid addition salts thereof.

Among the heterocyclic coupling agents applicable in the ready-to-usedye composition according to the invention, derivatives ofbenzimidazole, derivatives of benzomorpholine, derivatives of sesamol,pyrazolo-azol derivatives, pyrrolo-azole derivatives, imidazolo-azolederivatives, pyrazolo-pyrimidine derivatives, derivatives ofpyrazoline-3,5-diones, pyrrolo-[3,2-d]oxazole derivatives,pyrazolo-[3,4-d]-thiazole derivatives, thiazolo-azole S-oxidederivatives, thiazolo-azole S,S-dioxide derivatives and their additionsalts with an acid can in particular be mentioned.

Among the benzimidazole derivatives applicable as heterocyclic couplingagents in the dye composition according to the invention, the compoundsof the following formula (I) and their acid addition salts can inparticular be mentioned:

in which:

R₁ represents a hydrogen atom or C₁-C₄-alkyl,

R₂ represents a hydrogen atom, C₁-C₄alkyl or phenyl,

R₃ represents a hydroxyl, amino or methoxy group,

R₄ represents a hydrogen atom, a hydroxyl group, a methoxy group orC₁-C₄alkyl group,

with the proviso that:

when R₃ is an amino group, it is in position 4,

when R₃ is in position 4, R₄ is in position 7,

when R₃ is in position 5, R₄ is in position 6.

Among the benzimidazole derivatives of the above formula (I), thefollowing can in particular be mentioned: 4-hydroxy benzimidazole,4-amino benzimidazole, 4-hydroxy-7-methyl benzimidazole,4-hydroxy-2-methyl benzimidazole, 1-butyl-4-hydroxy benzimidazole,4-amino-2-methyl benzimidazole, 5,6-dihydroxy benzimidazole,5-hydroxy-6-methoxy benzimidazole, 4,7-dihydroxy benzimidazole,4,7-dihydroxy-1-methyl benzimidazole, 4,7-dimethoxy benzimidazole,5,6-dihydroxy-1-methyl benzimidazole, 5,6-dihydroxy-2-methylbenzimidazole, 5,6-dimethoxy benzimidazole and their addition salts withan acid.

Among the benzomorpholine derivatives applicable as heterocycliccoupling agents in the ready-to-use dye composition according to theinvention, the compounds of the following formula (II) and theiraddition salts with an acid can in particular be mentioned:

in which

R₅ and R₆, which are identical or differ, each represents a hydrogenatom or C₁-C₄-alkyl, and

Z represents a hydroxyl group or an amino group.

Among the benzomorpholine derivatives of the above formula (II) thefollowing can in particular be mentioned: 6-hydroxy 1,4-benzomorpholine,N-methyl 6-hydroxy 1,4-benzomorpholine, 6-amino 1,4-benzomorpholine andtheir acid addition salts.

Among the derivatives of sesamol applicable as heterocyclic couplingagents in the ready-to-use dye composition according to the invention,the compounds of the following formula (III) and their addition saltswith an acid can in particular be mentioned:

in which

R₇ represents a hydroxyl group, an amino group, a C₁-C₄-alkylaminogroup, a C₁-C₄monohydroxyalkylamino group or aC₂-C₄polyhydroxyalkylamino group,

R₈ represents a hydrogen atom, a halogen atom or a C₁-C₄alkoxy group.

Among the derivatives of sesamol of the above formula (III), thefollowing can in particular be mentioned: 2-bromo 4,5-methylenedioxyphenol, 2-methoxy 4,5-methylenedioxy aniline, 2-(β-hydroxyethyl)amino4,5-methylenedioxy benzene and their acid addition salts.

Among the pyrazolo-azole derivatives applicable as heterocyclic couplingagents in the ready-to-use dye composition according to the invention,the compounds can in particular be mentioned which are described in thefollowing Patents and Patent Applications: FR 2 075 583, EP-A-119 860,EP-A-285 274, EP-A-244 160, EP-A-578 248, GB 1 458 377, U.S. Pat. No.3,277,554, U.S. Pat. No. 3,419,391, U.S. Pat. No. 3,061,432, U.S. Pat.No. 4,500,630, U.S. Pat. No. 3,725,067, U.S. Pat. No. 3,926,631, U.S.Pat. No. 5,457,210, JP 84/99437, JP 83/42045, JP 84/162548, JP84/171956, JP 85/33552, JP 85/43659, JP 85/172982, JP 85/190779 as wellin the following publications: Chem. Ber. 32, 797, (1899), Chem. Ber.89, 2550, (1956), J. Chem. Soc. Perkin trans I, 2047, (1977), J. Prakt.Chem., 320, 533, (1978), the subject matter of which constitute anintegrated part of the present application.

As the pyrazolo-azole derivatives, the following can in particular bementioned:

2-methyl pyrazolo[1,5-b]-1,2,4-triazole,

2-ethyl pyrazolo[1,5-b]-1,2,4-triazole,

2-isopropyl pyrazolo[1,5-b]-1,2,4-triazole,

2-phenyl pyrazolo[1,5-b]-1,2,4-triazole,

2,6-dimethyl pyrazolo[1,5-b]-1,2,4-triazole,

7-chloro-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,

3,6-dimethyl-pyrazolo[3,2-c]-1,2,4-triazole,

6-phenyl-3-methylthio- pyrazolo[3,2-c]-1,2,4-triazole,

6-amino-pyrazolo[1,5-a]benzimidazole, and their addition salts with anacid.

Among the pyrrolo-azole derivatives applicable as heterocyclic couplingagents in the ready-to-use dye composition according to the invention,the compounds can in particular be mentioned which are described in thefollowing Patents and Patent Applications: U.S. Pat. No. 5,256,526,EP-A-557 851, EP-A-578 248, EP-A-518 238, EP-A-456 226, EP-A-488 909,EP-A-488 248 and in the following publications:

D. R. Liljegren Ber. 1964, 3436;

E. J. Browne, J.C.S., 1962, 5149;

P. Magnus, J.A.C.S., 1990, 112, 2465;

P. Magnus, J.A.C.S., 1987, 109, 2711;

Angew. Chem. 1960, 72, 956;

and Rec. Trav. Chim. 1961, 80, 1075, the subject matter of whichconstitute an integrated part of the present application.

As the pyrazolo-azole derivatives, the following can in particular bementioned:

5-cyano-4-ethoxycarbonyl-8-methyl pyrrolo [1,2-b]-1,2,4-triazole,

5-cyano-8-methyl-4-phenyl pyrrolo [1,2-b]-1,2,4-triazole,

7-amido-6-ethoxycarbonyl pyrrolo [1,2-a]-benzimidazole, and theiraddition salts with an acid.

Among the imidazolo-azole derivatives applicable as heterocycliccoupling agents in the ready-to-use dye composition according to theinvention, the compounds can in particular be mentioned which aredescribed in the following Patents and Patent Applications: U.S. Pat.No. 5,441,863, JP 62-279 337, JP 06-236 011 and JP 07-092 632, thesubject matter of which constitute an integrated part of the presentapplication.

As the imidazolo-azole derivatives, the following can in particular bementioned:

7,8-dicyano-imidazolo-[3,2-a]-imidazole,

7,8-dicyano-4-methyl-imidazolo -[3,2-a]-imidazole, and their additionsalts with an acid.

Among the pyrazolo-pyrimidine derivatives applicable as heterocycliccoupling agents in the ready-to-use dye composition according to theinvention, the compounds can in particular be mentioned which aredescribed in the following Patent Application: EP-A-304-001, the subjectmatter of which constitute an integrated part of the presentapplication.

As the pyrazolo-pyrimidine derivatives, the following can in particularbe mentioned:

pyrazolo-[1,5-a]-pyrimidine-7-one,

2,5-dimethyl pyrazolo [1,5-a] pyrimidine-7-one,

2-methyl-6-ethoxycarbonyl pyrazolo [1,5-a] pyrimidine-7-one,

2-methyl-5-methoxymethyl pyrazolo [1,5-a] pyrimidine-7-one,

2-tert-butyl-5-trifluoromethyl pyrazolo [1,5-a] pyrimidine-7-one,

2,7-dimethyl pyrazolo [1,5-a] pyrimidine-5-one, and their addition saltswith an acid.

Among the pyrazoline-3,5-diones derivatives applicable as heterocycliccoupling agents in the ready-to-use dye composition according to theinvention, the compounds can in particular be mentioned which aredescribed in the following Patents and Patent Applications: JP07-036159, JP 07-084348 and U.S. Pat. No. 4,128,425, and in thefollowing publications:

L. WYZGOWSKA, Acta. Pol. Pharm. 1982, 39 (1-3), 83.

E. HANNIG, Pharmazie, 1980, 35 (4), 231

M. H. ELNAGDI, Bull. Chem. Soc. Jap., 46(6), 1830, 1973

G. CARDILLO, Gazz. Chim. Ital. 1966, 96, (8-9), 973, the subject matterof which constitute an integrated part of the present application.

As the derivatives of pyrazolin-3,5-diones, the following can inparticular be mentioned:

5 1,2-diphenyl pyrazoline-3,5-dione,

1,2-diethyl pyrazoline-3,5-dione, and their addition salts with an acid.

Among the pyrrolo-[3, 2-d]-oxazole derivatives applicable asheterocyclic coupling agents in the ready-to-use dye compositionaccording to the invention, the compounds can in particular be mentionedwhich are described in the Patent Application JP 07-325 375, the subjectmatter of which constitute an integrated part of the presentapplication.

Among the pyrazolo-[3,4-d]-thiazole derivatives applicable asheterocyclic coupling agents in the ready-to-use dye compositionaccording to the invention, the compounds can in particular be mentionedwhich are described in the Patent Application JP 07-244 361 and in J.Heterocycl. Chem. 16, 13, (1979).

Among the thiazolo-azole S-oxide derivatives and thiazolo-azoleS,S-dioxide derivatives applicable as heterocyclic coupling agents inthe ready-to-use dye composition according to the invention, thecompounds can in particular be mentioned which are described in thefollowing documents:

JP 07-098 489;

Khim. Geterotsilk. Soedin, 1967, p. 93;

J. Prakt. Chem., 318, 1976, p. 12;

Indian J. Heterocycl. Chem. 1995, 5(2), p. 135;

Acta. Pol. Pharm. 1995, 52(5), 415;

Heterocycl. Commun. 1995, 1(4), 297;

Arch. Pharm. (Weinheim, Ger.), 1994, 327(12), 825.

These coupling agents constitute preferably between approximately0.0001% and approximately 10% by weight of the ready-to-use dyecomposition, especially between approximately 0.005% and approximately5% by weight.

The cationic direct dye(s) applicable in the ready-to-use dyecomposition according to the invention is/are preferably selected amongcationic amino-anthraquinone dyes, cationic mono or di-azo dyes andcationic naphtoquinone dyes.

Examples of the above areespecially[8-[(p-aminophenyl)azo]-7-hydroxy-2-naphtyl]trimethylammoniumchloride (also called Basic Brown 16 or Arianor Mahogany 306002 in ColorIndex),3-[(4-amino-6-bromo-5,8-dihydro-1-hydroxy-8-imino-5-oxo-2-naphtalenyl)amino]-N,N,N-trimethyl-benzeneaminiumchloride (also called Basic Blue 99 or Arianor Steel Blue 306004 inColor Index),7-hydroxy-8-[(2-methoxyphenyl)azo]-N,N,N-trimethyl-2-naphtaleneaminiumchloride (also called Basic Red 76 or Arianor Madder Red in ColorIndex),[8-[(4-amino-2-nitrophenyl)azo]-7-hydroxy-2-naphtyl]trimethylammoniumchloride (also called Basic Brown 17 or Arianor Sienna Brown 306001 inColor Index) and3-[(4,5-dihydro-3-methyl-5-oxo-1-phenyl-1H-pyrazol-4-yl)azo]-N,N,N-trimethyl-benzenaminiumchloride (also called Basic Yellow 57 or Arianor Straw Yellow 306005 inColor Index).

The cationic direct dye(s) can furthermore be selected among:

a) Compounds of the formula (V):

in which

D represents a nitrogen atom or a group —CH,

R₁₉ and R₂₀, which are identical or differ, each represents a hydrogenatom, a C₁-C₄alkyl group, which can be substituted with one of thegroups —CN, —OH or —NH₂ or together with a carbon atom in the benzenering form an optionally oxygen-containing or nitrogen-containingheterocyclic group, which can be substituted with one or more C₁-C₄alkylgroups; or a 4′-aminophenyl group,

R₂₁ and R₂₁, which are identical or differ, each represents a hydrogenatom or a halogen atom selected from chlorine, bromine, iodine andfluorine, cyano, C₁-C₄-alkoxy or acetyloxy, X⁻ represents an anion,preferably selected from chloride, methylsulphate and acetate,

A represents a group selected from the following structures A1-A19:

wherein R₂₂ represents a C₁-C₄alkyl group, which can besubstituted witha hydroxyl group, and R₂₃ represents a C₁-C₄alkoxy group;

b) compositions of the formula (VI):

in which

R₂₄ represents a hydrogen atom or a C₁-C₄alkyl group,

R₂₅ represents a hydrogen atom, an alkyl group, which can be substitutedwith a group —CN or with an amino group, or 4′-aminophenyl, or R₂₅represents together with R₂₄ an optionally oxygen and/ornitrogen-containing heterocyclic group, which can be substituted with aC₁-C₄alkyl group,

R₂₆ and R₂₇, which are identical or differ, represent a hydrogen atom, ahalogen atom such as bromine, chlorine, iodine or fluorine,

C₁-C₄alkyl, C₁-C₄alkoxy or the group —CN,

X⁻ represents an anion, preferably selected from chloride,methylsulphate and acetate,

B represents a group selected from the following structures B1-B6:

in which R₂₈ represents a C₁-C₄alkyl group, and R₂₉ and R₃₀, which areidentical or differ, each represents a hydrogen atom or a C₁-C₄alkylgroup;

c) compounds of the following formulae (VII) and (VII′):

in which

R₃₁ represents a hydrogen atom, a C₁-C₄alkoxy group, ahalogenatom suchas bromine, chlorine, iodine or fluorine, or an amino group,

R₃₂ represents a hydrogen atom or a C₁-C₄alkyl group, or R₃₂ togetherwith a carbon atom in the benzene ring forms a heterocyclic group, whichoptionally includes an oxygen atom and/or is substituted with one ormore C₁-C₄alkyl groups,

R₃₃ represents a hydrogen atom or a halogen atom such as bromine,chlorine, iodine or fluorine,

R₃₄ and R₃₅ , which are identical or differ, each represents a hydrogenatom or a C₁-C₄alkyl group,

D₁ and D₂, which are identical or differ, represent a nitrogen atom or agroup —CH,

m=0 or 1,

whereby it should be understood that when R₃₁ represents anon-substituted amino group, D₁ and D₂ represent simultaneously a group—CH, and m=0,

X⁻ represents an anion, preferably selected from chloride,methylsulphate and acetate,

E represents a group selected from the following structures E1-E8:

in which R₃₆ represents a C₁-C₄alkyl group;

when m=0 and D₁ represents a nitrogen atom, E can also represent a groupwith the following structure E9:

in which R₃₆ represents a C₁-C₄alkyl group.

The cationic direct dyes of the formulae (V), (VI), (VII) and (VII′),which are applicable in the ready-to-use dye compositions according tothe invention, are compositions known per se, which are described forinstance in the Patent Applications WO 95/01772, WO 95/15144 and EP-A-0714 954.

Among the cationic direct dyes of the formula (V), which are applicablein the ready-to-use dye compositions according to the invention, thecompounds of the following structures (V1) to (V52) can in particular bementioned:

Among the above compounds with the structures (V1) to (V52), thecompounds with the structures (V1), (V2), (V4), (V14) and (V31) areparticularly preferred.

Among the cationic direct dyes of the formula (VI), which are applicablein the ready-to-use dye compositions according to the invention, thecompounds with the following structures (VI1) to (VI12) can inparticular be mentioned:

Among the cationic direct dyes of the formula (VII), which areapplicable in the ready-to-use dye compositions according to theinvention, the compounds with the following structures (VII1) to (VII18)can in particular be mentioned:

Among the above particular compositions with the structures (VII1) to(VII18), the compounds with the structures (VII4), (VII5) and (VII13)are particularly preferred.

Among the cationic direct dyes of the formula (VII′), which areapplicable in the ready-to-use dye compositions according to theinvention, the compounds with the following structures (VII′1) to(VII′3) can in particular be mentioned:

The cationic direct dye or dyes used according to the inventionrepresent preferably between approximately 0.001% and approximately 10%by weight of the total weight of the ready-to-use dye composition,especially between approximately 0.05% and approximately 5% by weight.

In general, the acid addition salts suitable within the scope of the dyecompositions according to the invention (oxidation bases and couplingagents) are especially selected from hydrochlorides, hydrobromides,sulphates, tartrates, lactates and acetates.

With regard to laccase which is an oxidase used in the presentinvention, there is no particular limitation for its source, etc. butthose derived from microorganisms are preferred. Among them, laccasederived from genus Myceliophthora or Scytalidium is preferred. Thecompounding amount of laccase in the composition of the presentinvention varies depending upon dosage form, frequency and treating timeof the preparation and upon titer of the enzyme preparation but,usually, it is 0.0005-20% or, preferably, 0.005-10%. When the amount isless than 0.0005%, a sufficient effect is not resulted while, even whenit is more than 20%, an increase in the effect proportional to theincrease of the amount is not achieved.

Particularly preferred enzymes are laccases and related enzymes, theterm “laccases and related enzymes” including enzymes comprised by theenzyme classification E. C. 1.10.3.2 (laccases) and catechol oxidaseenzymes comprised by E. C. 1.10.3.1, bilirubin oxidase enzymes comprisedby the enzyme classification E. C. 1.3.3.5 and mono-phenolmono-oxygenase enzymes comprised by the enzyme classification E. C.1.14.99.1. Laccases are multi-copper containing enzymes that catalyzethe oxidation of phenols and aromatic amines. Laccase-mediatedoxidations result in the production of aryloxy-radical intermediatesfrom suitable phenolic substrates; the ultimate coupling of theintermediates so produced provides a combination of dimeric, oligomeric,and polymeric reaction products.

The laccase may be derived from a microorganism, e.g. a fungus or abacteria, or a plant. Preferably, the laccase employed is derived from afungus. More preferably, it is derived from a strain of Polyporus sp.,in particular a strain of P. pinsitus or P. versicolor, a strain ofMyceliophthora sp., e.g. M. thermophila, a strain of Rhizoctonia sp., inparticular a strain of Rh. praticola or Rh. solani, a strain ofPyricularia sp, in particular P. oryzae, or a strain of Scytalidium,such as S. thermophilium. The laccase may also be from a plant such asRhus sp., e.g. Rhus vernicifera,

In specific embodiments of the invention the oxidoreductase is a laccasesuch as a Polyporus sp. laccase, especially the Polyporus pinisituslaccase (also called Trametes villosa laccase) described in WO 96/00290(from Novo Nordisk Biotec Inc.) or a Myceliophthora sp. laccase,especially the Myceliophthora thermophila laccase described in WO95/33836 (from Novo Nordisk Biotech Inc.).

Further, the laccase may be a Scytalidium sp. laccase such as the S.thermophilium laccase described in WO 95/33837 and WO 97/19998 (fromNovo Nordisk Biotech Inc.), the contents of which is incorporated hereinby reference, or a Pyricularia sp. laccase, such as the Pyriculariaoryzae laccase which can be purchased from SIGMA under the trade nameSIGMA No. L5510, or a Coprinus sp. laccase, such as a C. cinereuslaccase, especially a C. cinereus IFO 30116 laccase, or a Rhizoctoniasp. laccase, such as a Rh. solani laccase, especially the neutral Rh.solani laccase described in WO 95/07988 (from Novo Nordisk A/S) having apH optimum in the range of from 6.0 to 8.5.

The laccase may also be derived from a fungus such as Collybia, Fomes,Lentinus, Pleurotus, Aspergillus, Neurospora, Podospora, Phlebia, e.g.P. radiata (WO 92/01046), Coriolus sp., e.g. C. hirsitus (JP 2-238885),or Botrytis.

Bilirubin oxidase may preferably be derived from a strain of Myrotheciumsp., such as M. verrucaria.

Oxidases yielding peroxide (H₂O₂) are typically used in combination witha peroxidase to remove or at least reduce the peroxide produced.

Suitable oxidases include glucose oxidase (E. C. 1.1.3.4), hexoseoxidase (E. C. 1.1.3.5), L-amino-acid oxidase (E. C. 1.4.3.2), xylitoloxidase, galactose oxidase (E. C. 1.1.3.9), pyranose oxidase (E. C.1.1.3.10) and alcohol oxidase (E. C. 1.1.3.13).

If an L-amino acid oxidase is used, it may be derived from a Trichodermasp. such as Trichodezma harzianum, such as the L-amino acid oxidasedescribed in WO 94/25574 (from Novo Nordisk A/S), or Trichodezma viride.

A suitable glucose oxidase may originate from Aspergillus sp., such as astrain of Aspergillus niger, or from a strain of Cladosporium sp. inparticular Cladosporium oxysporum.

Hexose oxidases from the red sea-weed Chondrus crispus (commonly knownas Irish moss) (Sullivan and Ikawa, (1973), Biochim. Biophys. Acts, 309,p. 11-22; Ikawa, (1982), Meth. in Enzymol. 89, Carbohydrate MetabolismPart D, 145-149) oxidise a broad spectrum of carbohydrates, such asD-glucose, D-galactose, maltose, cellobiose, lactose, D-glucose6-phosphate, D-mannose, 2-deoxy-D-glucose, 2-deoxy-D-galactose,D-fructose, D-glucuronic acid, and D-xylose.

Further, in addition to the above-mentioned components, it is alsopossible, if necessary, to add pH buffers, surface-active agents,thickeners such as hydroxyethyl cellulose and xanthan gum, perfumes,antiseptics, ultraviolet ray absorbers, antioxidants, bactericides,pearling agent, etc. With regard to the surface-active agents among theabove, any of anionic ones such as α-olefinsulfonates, alkanesulfonates,fatty acid alkyl ether carboxylates, N-acylamino acids and C₁₂₋₁₈saturated and unsaturated fatty acid acylglutamate esters; amphotericones such as alkylbetaines, alkylamidobetaines and hydroxysulfobetaines;cationic ones such as mono- or di-alkyl quaternary ammonium salts; andnonionic ones such as polyoxyethylene alkyl ethers and fatty acidalkylolamides may be used.

In order to improve the feel or touch of the hair, it is also possibleto compound silicone derivatives such as dimethylpolysiloxane,amino-modified silicone and polyether-modified silicone.

The hairdye composition of the present invention may be prepared intoany of dosage forms of liquid, cream, gel, aerosol, etc. and, in thatcase, it is preferred to prepare into a single preparation type in viewof usability, etc.

In the preparation of the composition by compounding the above-mentionedcomponents, it is preferred that the compounding is carried out in vacuaor in an atmosphere of inert gas such as nitrogen gas, carbon dioxidegas or rare gas. With regard to a method for compounding, any methodwill do and there is no particular limitation therefor. Examples are amethod where vacuation is conducted, a method where substitution withnitrogen gas is conducted and a method where vacuation is conductedfollowed by substituting with inert gas.

It is particularly preferred that the composition of the presentinvention is made into a form of aerosol and, when made into an aerosolform, it is preferred to carry out a shaking operation during and/orimmediately after charging a propellant. This is an operation wherebythe residual oxygen in a container is compulsorily consumed andformation of a dye precursor is suppressed. Thus, by such an operation,insolubilization and aggregation of the dye in the system do not occurwhereby stability becomes good. Method for the shaking may be any ofmeans of up-and-down, horizontal, turning and the shape of the FIG. 8and there is no particular limitation therefor. Time for shaking may bedependent upon the type and is from 10 seconds to 30 minutes or,preferably, 1-10 minute(s).

The propellant may be any of liquefied propane gas (LPG), dimethyl ether(DME), nitrogen gas, carbon dioxide gas, etc. and, in view of productionof foams after spraying, LPG is preferred.

Charging of the propellant may be carried out in air although it ispreferred to charge in vacuo or in an atmosphere of inert gas such asnitrogen gas, carbon dioxide gas and rare gas. With regard to a methodtherefor, any method will do and there is no particular limitation.

The pH of the hairdye composition of the present invention is preferably5.0-9.5 or, more preferably, 6.0-8.0. When the pH is higher than 9.5,there may be a case where a problem of irritation occurs.

EXAMPLES

The present invention will now be specifically illustrated by way of thefollowing Examples and Comparative Examples although the presentinvention is not limited thereto. In the following examples, % meansthat by weight. Methods for testing the properties used in the followingexamples are as follows.

Skin Irritation:

The test was carried out according to a method by Kimber, et al(Toxicol. Lett. , 55:203-213, 1991) and Hostineck, et al. (Arch.Dermatol. Res., 287:567-571, 1995) which have been used as animalsubstitution methods for the evaluation of sensitivity. Thus, adeveloper substance was dissolved in a mixture of acetone and olive oil(in a mixing ratio of 4:1) to an extent of 2% and the solution wasapplied to skin of the back of a Balb/c mouse of eight weeks age. Afterfive days from the application, lymph node was taken out from thetreated mouse and then lymphoid cells were suspended in a PRMI 1640medium to which autoserum was added whereupon a lymphoid cell solutionwas prepared.

The resulting lymphoid cells were incubated at 37° C. for three days inthe presence of 5% of CO₂ and the growing activity of the incubatedsolution was measured. Degree of sensitivity was judged by calculatingthe sensitivity index from the following formula followed by referringto the following criteria.

Sensitivity Index=(Growing Activity of Lymphoid Cells of Mice Appliedwith the Substance to be Evaluated)/(Growing Activity of Lymphoid Cellsof Mouse Applied with Acetone-Olive Oil Mixture)

Sensitivity Degree Sensitivity Index ∘∘ very weak 1.0 or more but lessthan 1.25 ∘ weak 1.25 or more but less than 1.5 Δ somewhat 1.5 or morebut less than 1.75 weak x strong 1.75 or more

Hair-dying Property (ΔE):

About 10 g of a dried tuft of white hair of goat were shampooed, waterwas removed therefrom (weight of the tuft after removing the water was17 g) and each 3 g of the compositions to be evaluated (the productsimmediately after the compounding) were applied thereto quickly anduniformly. This was allowed to stand at 30° C. for a predeterminedperiod, rinsed, dried, shampooed and air-dried and a hair-dyeingproperty to the hair of goat was evaluated.

With regard to the hair-dyeing property (ΔE), the L, a and b values ofthe dyed tuft were measured by a color difference meter (SE2000manufactured by Nippon Denshoku) and the color difference (ΔE) from thehair which was not dyed was calculated whereby the hair-dyeing propertywas evaluated. Incidentally, the more the ΔE, the better the hair dyeingproperty.

EXAMPLES AND COMPARATIVE EXAMPLES

A hairdye composition of a single preparation type having the followingformulation was prepared and its properties were evaluated. The resultis shown in Table 2.

Compounded Components Amount (%) Example 1 (Gel Type)5,6-Dihydroxyindoline.HBr 3 Laccase (from genus Myceliophthora) 0.5Xanthan gum 0.5 Hydroxyethyl cellulose 0.5 Ethanol 5.0 Pure waterbalance Total 100.0 pH (as adjusted by NaOH) 7.0 Example 2 (Gel Type)5,6-Dihydroxyindoline.HBr 2 Toluene-2,5-diamine sulfate 0.01p-Aminophenol 0.01 Laccase (from genus Scytalidium) 0.5 Xanthan gum 0.5Hydroxyethyl cellulose 0.5 Ethanol 5.0 Pure water balance Total 100.0 pH(as adjusted by NaOH) 7.0 Comparative Example 1 (Gel Type)Toluene-2,5-diamine 3 p-Aminophenol 1 Laccase (from genusMyceliophthora) 0.5 Xanthan gum 0.5 Hydroxyethyl cellulose 0.5 Ethanol5.0 Pure water balance Total 100.0 pH (as adjusted by NaOH) 7.0 Example3 (Cream Type) 5,6-Dihydroxyindoline.HBr 3 Decaglyceryl monostearate 3Cetostearyl alcohol 0.5 Stearic acid 0.8 Xanthan gum 1 Laccase (fromgenus Myceliophthora) 1 Carboxymethyl cellulose 1 Sodium hydroxide q.s.Pure water balance Total 100.0 pH (as adjusted by NaOH) 7.0 Example 4(Cream Type) 5,6-Dihydroxyindoline.HBr 3 POE(10) Cetyl ether 8 Stearylalcohol 2.5 Oleyl alcohol 5 Behenyl alcohol 2 Cetyl alcohol 2Stearyltrimethylammonium chloride 1 Laccase (from Japanese lacquer tree)1 Glycerol 2 Triethanolamine q.s. Pure water balance Total 100.0 pH (asadjusted by NaOH) 7.0 Comparative Example 2 (Cream Type)Toluene-2,5-diamine sulfate 3 p-Aminophenol 1 Decaglyceryl monostearate3 Cetostearyl alcohol 0.5 Stearic acid 0.8 Laccase (from genusMyceliophthora) 1 Carboxymethyl cellulose 1 Sodium hydroxide q.s. Purewater balance Total 100.0 pH (as adjusted by NaOH) 7.0

TABLE 1 (Aerosol Type) Examples Comp. Ex.s Components (%) 5 6 7 8 9 1011 3 4 5 5,6-Dihydroxyindoline.HBr 3 2 3 1 2 2 1.5 — — —Toluene-5,6-diamine sulfate — — — — — 0.01 — 3 3 3 p-Aminophenol — — — —— 0.01 0.01 2 1 2 m-Phenylenediamine — — — — — — 0.01 — 0.5 — Resorcinol— — — — — — 0.01 0.5 1 0.5 Ethanol 5 5 5 5 5 5 5 5 5 5 POE Lauryl ethersodium sulfate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Coconut oil fattyacid diethanolamide 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Laccase(genus Myceliophthora) 0.5 0.05 — 1 — 0.5 — 0.5 — — Laccase (genusScytalidium) — — 1 — 0.5 — 0.5 — — 0.5 Sodium hydroxide q.s. q.s. q.s.q.s. q.s. q.s. q.s. q.s. q.s q.s LPG (4 kg/cm²) 4 4 4 4 4 4 4 4 4 4 Purewater b b b b b b b b b b Total 100.0 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 100.0 pH 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 bbalance

TABLE 2 Examples Comp.Ex. 1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 SkinIrritation ∘∘ ∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ x x x x x Dyeing Prop(ΔE) 28 3029 27 31 28 30 27 28 30 29 31 29 30 14 28

A hairdye composition of the present invention exhibits little skinirritation and has an excellent hair dyeing effect.

What is claimed is:
 1. A hair dye composition in the form of an aerosolof one-pack type comprising: 5,6-dihydroxyindoline or its salt; alaccase; water; and a propellant; wherein said hair dye composition hasa pH of 5.0 to 9.5, and a shaking operation is carried out during,immediately, or during and immediately after charging the propellant sothat the residual oxygen is consumed and the formation of a dyeprecursor is suppressed.
 2. The hair dye composition of claim 1, saidhair dye composition further comprising at least one more indoline orindoline compound.
 3. The hair dye composition of claim 1, wherein theconcentration of said 5,6-dihydroxyindoline or its salt is 0.01-30% byweight of said hair dye composition.
 4. The hair dye composition ofclaim 1, further comprising an oxidation dye selected from the groupconsisting of 5-amino-o-cresol, o-aminophenol, m-aminophenol,p-aminophenol, 2,6-diaminopyridine,5-(2-hydroxylethylamino)-2-methylphenol,N,N-bis(β-hydroxyl)-p-phenylenediamine sulfate,p-nitro-o-phenylenediamine, p-phenylenediamine, m-phenylenediamine,N-phenyl-p-phenylenediamine, resorcinol,2-hydroxyl-5-nitro-2′,4′-diaminoazobenzene sodium sulfate,toluene-2,5-diamine, 5-amino-o-cresol sulfate, p-aminophenol sulfate,o-chloro-p-phenylenediamine sulfate, 4,4′-diaminodiphenylamine sulfate,p-methylaminophenol sulfate, p-phenylenediamine sulfate,m-phenylenediamine sulfate, toluene-2,5-diamine sulfate,2,4-diaminophenoxyethanol hydrochloride, toluene-2,5-diaminehydrochloride, m-phenylenediamine hydrochloride, 2,4-diamrinophenolhydrochloride, 3,3′-iminodiphenol, p-phenylenediamine hydrochloride,N-phenyl-p-phenylenediamine hydrochloride, N-phenyl-p-phenylenediamineacetate, 1,5-dihydroxynaphthalene, toluene-3,4-diamine,p-methylaminophenol,N,N′-bis(4-aminophenyl)-2,5-diamino-1,4-quinonediimine, o-aminophenolsulfate, 2,4-diaminophenyl sulfate and m-aminophenol sulfate.
 5. Thehair dye composition of claim 1, further comprising an oxidation baseselected from the group consisting of a para-phenylenediamine, a doublebase, a para-aminophenol, an ortho-aminophenol and a heterocyclicoxidation base.
 6. The hair dye composition of claim 5, wherein saidpara-phenylenediamine as the oxidation base is selected from the groupconsisting of para-phenylenediamine, paratoluylenediamine, 2-isopropylpara-phenylenediamine, 2-0-hydroxyethyl para-phenylenediamine,2-β-hydroxyethyloxy para-phenylenediamine, 2,6-dimethylpara-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,3-dimethylpara-phenylenediamine, N,N-bis-(β-hydroxyethyl) para-phenylenediamine,2-chloro para-phenylenediamine, 2-β-acetylaminoethyloxypara-phenylenediamine and acid addition salts thereof.
 7. The hair dyecomposition of claim 5, wherein said double base as the oxidation baseis selected from the group consisting of N,N=-bis-(β-hydroxyethyl)N,N′-bis-(4′-aminophenyl) 1,3-diamino propanol,N,N=-bis-(β-hydroxyethyl) N,N=-bis-(4′-aminophenyl) ethylenediamine,N,N=-bis-(4-aminophenyl) tetramethylenediamine,N,N′-bis-(β-hydroxyethyl) N,N′-bis-(4-aminophenyl)tetramethylenediamine, N,N′-bis-(4-methylaminophenyl)tetramethylenediamine, N,N′-bis-(ethyl) N,N′-bis-(4′-amino,3-methylphenyl) ethylenediamine,1,8-bis-(2,5-diaminophenoxy)-3,5-dioxaoctane and acid addition saltsthereof.
 8. The hair dye composition of claim 5, wherein saidpara-aminophenol as the oxidation base is selected from the groupconsisting of para-aminophenol, 4-amino 3-methyl phenol, 4-amino3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methylphenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol,4-amino 2-aminomethyl phenol, 4-amino 2-(β-hydroxyethyl aminomethyl)phenol, 4-amino 2-fluoro phenol and acid addition salts thereof.
 9. Thehair dye composition of claim 5, wherein said ortho-aminophenol as theoxidation base is selected from the group consisting of 2-amino phenol,2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-aminophenol and acid addition salts thereof.
 10. The hair dye composition ofclaim 5, wherein said heterocyclic oxidation base is selected from thegroup consisting of pyridine derivatives, pyrimidine derivatives,pyrazole derivatives, pyrazolo-pyrimidine derivatives and acid additionsalts thereof.
 11. The hair dye composition of claim 5, wherein saidoxidation base or bases is 0.0005% to 12% by weight of said hair dyecomposition.
 12. The hair dye composition of claim 1, further comprisinga coupling agent selected from the group consisting of2-methyl-5-amino-phenol, 5-N-(β-hydroxyethyl)-amino-2-methyl-phenol,3-amino-phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methyl-benzene,4-chloro-1,3-dihydroxy-benzene,2,4-diamino-1-(β-hydroxyethyloxy)-benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxy-benzene, 1,3-diamino-benzene,1,3-bis-(2,4-diaminophenoxy)-propane, sesamol, α-naphtol,6-hydroxy-indole, 4-hydroxy-indole, 4-hydroxy-N-methyl-indole,6-hydroxy-indolin, 2,6-dihydroxy-4-methyl-pyridine,1-H-3-methyl-pyrazole-5-on, 1-phenyl-3-methyl-pyrazole-5-one,2,6-dimethyl-1,2,4-triazole, 2,6-dimethyl-1,2,4-triazole,6-methyl-pyrazolo-benzimidazole and acid addition salts thereof.
 13. Thehair dye composition of claim 12, wherein said coupling agent or agentsis 0.0001% to 10% by weight of said hair dye composition.
 14. The hairdye composition of claim 1, further comprising a cationic direct dye.15. The hair dye composition of claim 1, wherein said laccase is 0.0005to 20% by weight of said hair dye composition.
 16. The hair dyecomposition of claim 1, further comprising at least one ingredientselected from the group consisting of a pH buffer, a surface-activeagent, a thickener, a perfume, an antiseptic, an ultraviolet rayabsorber, an antioxidant, a bactericide, a pearling agent and a siliconederivative.
 17. The hair dye composition of claim 1, wherein said pH is6.0 to 8.0.
 18. A method of making a hair dye composition in the form ofam erosol of one-pack type comprising: preparing said hair dyecomposition by compounding a composition comprising5,6-dihydroxyindoline or its salt, laccase, and water; placing said hairdye composition in a container; charging a propellant in said containerin vacuo or in an atmosphere of inert gas to form an aerosol of one-packtype; and shaking said aerosol of one-pack type during, immediately, orduring and immediately after charging the propellant, wherein saidshaking consumes the residual oxygen and suppresses the formation of adye precursor in said aerosol of one-pack type.
 19. The hair dyecomposition of claim 1, wherein said laccase is derived from amicroorganism.
 20. The hair dye composition of claim 19, wherein saidlaccase is derived from a fungus.
 21. The hair dye composition of claim20, wherein said laccase is derived from a strain of Polyporus sp.